Structural diversity of lanthanoid salicylate hydrates

Thomas Behrsing, Glen B. Deacon, Jenny Luu, Peter C. Junk, Brian W Skelton, Allan H White

Research output: Contribution to journalArticleResearchpeer-review

Abstract

From metathesis reactions between lanthanoid salts and sodium salicylate (Na(salH)) in water, four classes of lanthanoid salicylate hydrates have been identified. Single crystal X-ray studies established a new monomeric class [Ln(salH)3(H2O)3]·3H2O (6Ln). This new rhombohedral R3c, Z = 6 form ‘6Ln’ has the nine coordinate metal atom on a crystallographic 3-axis, for Ln = Sm–Gd, Ho, Er, Yb, Lu, Y. We also have augmented or defined the previously known different forms, consolidating or extending their putative ‘domains of existence’. The monohydrate, Ln = ‘1Ce’, monoclinic, P21/n, has been re-examined at low-temperature suggesting further elasticity in its formulation beyond the recently proposed ‘[Ln(H2sal)(Hsal)(sal)H2O)](∞|∞)’ for the Ln = Gd complex, ‘1Gd’, one of the protonic hydrogen atoms being associated with a very short phenoxyl–O⋯carboxylate–O distance (2.427(3) Å). With refinement and the insights from a previous Ln = Eu study, suggest the protonic disposition to be around the O⋯O median. The ‘domain of existence’ for this form embraces Ln = La (dependent on a powder diffraction study) – Gd. The tetrahydrate is manifested in two forms: triclinic, centrosymmetric binuclear [Ln2(salH)6(H2O)4]·4H2O, P1¯, Z = 1, ‘4Ln’ recorded here in a 153 K determination, for Ln = Ho, consolidating the assignment of its domain of existence to be Ho–Er, Y, and ‘polymeric mononuclear’ [Ln(salH)3(H2O)2](∞|∞)·2H2O, ‘4Ln,’ recorded here for Ln = Tb–Er, Yb, Lu, Y. The 6Gd hexahydrate shows paramagnetic f7 magnetic behaviour. The reaction conditions leading to the isolation of a particular structural type of lanthanoid salicylate could not be reliably identified, indicating that a fine balance exists in the preferential crystallization of the lanthanoid salicylate hydrate phases. The discovery of the monomeric class has applications for the species acting as a corrosion inhibitor in dilute aqueous solution.

Original languageEnglish
Pages (from-to)69-81
Number of pages13
JournalPolyhedron
Volume120
DOIs
Publication statusPublished - 14 Dec 2016

Keywords

  • Carboxylate
  • Crystal structure
  • Lanthanoid
  • Monomer
  • Salicylate

Cite this

Behrsing, T., Deacon, G. B., Luu, J., Junk, P. C., Skelton, B. W., & White, A. H. (2016). Structural diversity of lanthanoid salicylate hydrates. Polyhedron, 120, 69-81. https://doi.org/10.1016/j.poly.2016.05.047
Behrsing, Thomas ; Deacon, Glen B. ; Luu, Jenny ; Junk, Peter C. ; Skelton, Brian W ; White, Allan H. / Structural diversity of lanthanoid salicylate hydrates. In: Polyhedron. 2016 ; Vol. 120. pp. 69-81.
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Behrsing, T, Deacon, GB, Luu, J, Junk, PC, Skelton, BW & White, AH 2016, 'Structural diversity of lanthanoid salicylate hydrates' Polyhedron, vol. 120, pp. 69-81. https://doi.org/10.1016/j.poly.2016.05.047

Structural diversity of lanthanoid salicylate hydrates. / Behrsing, Thomas; Deacon, Glen B.; Luu, Jenny; Junk, Peter C.; Skelton, Brian W; White, Allan H.

In: Polyhedron, Vol. 120, 14.12.2016, p. 69-81.

Research output: Contribution to journalArticleResearchpeer-review

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T1 - Structural diversity of lanthanoid salicylate hydrates

AU - Behrsing, Thomas

AU - Deacon, Glen B.

AU - Luu, Jenny

AU - Junk, Peter C.

AU - Skelton, Brian W

AU - White, Allan H

PY - 2016/12/14

Y1 - 2016/12/14

N2 - From metathesis reactions between lanthanoid salts and sodium salicylate (Na(salH)) in water, four classes of lanthanoid salicylate hydrates have been identified. Single crystal X-ray studies established a new monomeric class [Ln(salH)3(H2O)3]·3H2O (6Ln). This new rhombohedral R3c, Z = 6 form ‘6Ln’ has the nine coordinate metal atom on a crystallographic 3-axis, for Ln = Sm–Gd, Ho, Er, Yb, Lu, Y. We also have augmented or defined the previously known different forms, consolidating or extending their putative ‘domains of existence’. The monohydrate, Ln = ‘1Ce’, monoclinic, P21/n, has been re-examined at low-temperature suggesting further elasticity in its formulation beyond the recently proposed ‘[Ln(H2sal)(Hsal)(sal)H2O)](∞|∞)’ for the Ln = Gd complex, ‘1Gd’, one of the protonic hydrogen atoms being associated with a very short phenoxyl–O⋯carboxylate–O distance (2.427(3) Å). With refinement and the insights from a previous Ln = Eu study, suggest the protonic disposition to be around the O⋯O median. The ‘domain of existence’ for this form embraces Ln = La (dependent on a powder diffraction study) – Gd. The tetrahydrate is manifested in two forms: triclinic, centrosymmetric binuclear [Ln2(salH)6(H2O)4]·4H2O, P1¯, Z = 1, ‘4Ln’ recorded here in a 153 K determination, for Ln = Ho, consolidating the assignment of its domain of existence to be Ho–Er, Y, and ‘polymeric mononuclear’ [Ln(salH)3(H2O)2](∞|∞)·2H2O, ‘4Ln,’ recorded here for Ln = Tb–Er, Yb, Lu, Y. The 6Gd hexahydrate shows paramagnetic f7 magnetic behaviour. The reaction conditions leading to the isolation of a particular structural type of lanthanoid salicylate could not be reliably identified, indicating that a fine balance exists in the preferential crystallization of the lanthanoid salicylate hydrate phases. The discovery of the monomeric class has applications for the species acting as a corrosion inhibitor in dilute aqueous solution.

AB - From metathesis reactions between lanthanoid salts and sodium salicylate (Na(salH)) in water, four classes of lanthanoid salicylate hydrates have been identified. Single crystal X-ray studies established a new monomeric class [Ln(salH)3(H2O)3]·3H2O (6Ln). This new rhombohedral R3c, Z = 6 form ‘6Ln’ has the nine coordinate metal atom on a crystallographic 3-axis, for Ln = Sm–Gd, Ho, Er, Yb, Lu, Y. We also have augmented or defined the previously known different forms, consolidating or extending their putative ‘domains of existence’. The monohydrate, Ln = ‘1Ce’, monoclinic, P21/n, has been re-examined at low-temperature suggesting further elasticity in its formulation beyond the recently proposed ‘[Ln(H2sal)(Hsal)(sal)H2O)](∞|∞)’ for the Ln = Gd complex, ‘1Gd’, one of the protonic hydrogen atoms being associated with a very short phenoxyl–O⋯carboxylate–O distance (2.427(3) Å). With refinement and the insights from a previous Ln = Eu study, suggest the protonic disposition to be around the O⋯O median. The ‘domain of existence’ for this form embraces Ln = La (dependent on a powder diffraction study) – Gd. The tetrahydrate is manifested in two forms: triclinic, centrosymmetric binuclear [Ln2(salH)6(H2O)4]·4H2O, P1¯, Z = 1, ‘4Ln’ recorded here in a 153 K determination, for Ln = Ho, consolidating the assignment of its domain of existence to be Ho–Er, Y, and ‘polymeric mononuclear’ [Ln(salH)3(H2O)2](∞|∞)·2H2O, ‘4Ln,’ recorded here for Ln = Tb–Er, Yb, Lu, Y. The 6Gd hexahydrate shows paramagnetic f7 magnetic behaviour. The reaction conditions leading to the isolation of a particular structural type of lanthanoid salicylate could not be reliably identified, indicating that a fine balance exists in the preferential crystallization of the lanthanoid salicylate hydrate phases. The discovery of the monomeric class has applications for the species acting as a corrosion inhibitor in dilute aqueous solution.

KW - Carboxylate

KW - Crystal structure

KW - Lanthanoid

KW - Monomer

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